Electrochemical Deoxygenation Process for Bio-oil Upgrading

CAAFI R&D Webinar Series S. (Elango) Elangovan

Joseph Hartvigsen Lyman Frost

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• Founded 1976 • Subsidiary Company of Keystone Holdings

(Coors Family owned) • 140,000 ft2 R&D and Manufacturing Facility • 150 Employees • Concept to commercialization

– R&D --> prototype --> pilot scale fabrication • Core competencies:

– Electrochemistry, Ionic conducting ceramics, & Advanced Materials

• Customers – 50% Fortune 100/500 Companies – 50% Govt.

Ceramatec Overview

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Ceramatec Technology Focus

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• Combining Electrochemistry, Ceramics, Advanced Materials, and Novel Fabrication: – Energy Conversion/Storage

• Solid Oxide Fuel Cells/Electrolyzer • Batteries

– Chemical Synthesis • Na, Li metal • Na methylate, Na hypochlorite • High purity oxygen, hydrogen

Ceramatec Technology Focus

– Fuel Synthesis/Processing • Biofuels and Methane to Liquid fuels • Heavy oil upgrading • Direct methane to chemical • Biogas clean up

– Environmental • Fly ash treatment • Na removal from radioactive waste

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Recent Project Awards • ARPA-E

– Intermediate Temperature Fuel Cell (2012) – Direct Conversion of Natural Gas to Chemical (2012) – Li-S Battery (2013)

• USDA – Biomass to Fuel

• DOE – Bio-oil Upgrading

• State of Wyoming/Office of Naval Research (2011/2013) – Modular Fischer Tropsch Demonstration

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Overview of Biofuel Technologies

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Biofuel Synthesis

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Electrochemical Deoxygenation of Pyrolysis Oil • DOE CHASE Project • Electric Energy input, No hydrogen • TRL 2

Electrochemical Hydrocarbon Coupling • USDA • Electric Energy input, No hydrogen, Hydrogen byproduct • TRL 3 - 4

Biogas to Liquids • DOE/ONR/Private • Biogas tar clean up, Fischer Tropsch(Gas to Liquids) • TRL 6

CHASE Project Team • Ceramatec

– Electrochemical Technology Development • Dr. S (Elango) Elangovan – PI • Mr. Joseph Hartvigsen – Chemical Engineer

• Pacific Northwest National Laboratory – Bio-oil Expertise and DeOx Integration test

• Mr. Douglas Elliott

• Drexel University – Lifecycle Analysis

• Dr. Sabrina Spatari

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Fast Pyrolysis of Biomass to Bio-oil for Liquid Fuels Production DOUGLAS C. ELLIOTT Pacific Northwest National Laboratory Ceramatec Salt Lake City, Utah December 6, 2013

Relationship of Fuel Compositions

Targets: H/C = 1.6 – 2.1 O/C = 0.02 – ?

0.0

0.5

1.0

1.5

2.0

0.0 0.2 0.4 0.6 0.8 1.0

H/C

O/C

SoftwoodHardwoodAgricultural Residue

Biomass Feedstock

Crude oil

Typical Pyrolysis Process

www.honeywellnow.com The Practical, Proven Path to Green Energy. 2010. Envergent Technologies.

Conditions to Maximize Bio-oil Production Liquid intermediates from the degradation of hemicellulose, cellulose, and lignin in particles of 2-4 mm, <10% moisture Fast Pyrolysis: 450°C < T < 550°C, t@T < 2 sec

Time

Tem

pera

ture

ΔtH

T

ΔtQ

Δt@TAs Δt@T ↑: Gas ↑ Oil ↓

As ΔtH ↑: Char ↑ Oil ↓

As ΔtQ ↑: Gas ↑ Oil ↓

Comparison of Wood-Derived Bio-oils and Petroleum Fuel

Characteristic Fast pyrolysis Bio-oil Wet --------- Dry

Heavy petroleum fuel

Water content, wt% 15-25 0.1 Insoluble solids, % 0.5-0.8 0.01% Carbon, % 39.5 55.8 85.2 Hydrogen, % 7.5 6.1 11.1 Oxygen, % 52.6 37.9 1.0 H/C 2.3 1.3 1.6 O/C 1.0 0.5 0.01 Nitrogen, % <0.1 0.3 Sulfur, % <0.05 2.3 Ash 0.2-0.3 <0.1 HHV, MJ/kg 17 40 Density, g/ml 1.23 0.94 Viscosity, cp 10-150@50ºC 180@50ºC

Bio-oil Composition Quick Check

0.0

0.5

1.0

1.5

2.0

0.0 0.2 0.4 0.6 0.8 1.0

H/C

O/C

SoftwoodHardwoodAgricultural ResiduePNNL FP Bio-oils

Biomass Feedstock

Flash Pyrolysis Bio-oils

Crude oil

Feedstock H/C O/C Softwood Forest Residue 1.05 0.38

Mtn Pine Beetle Killed 1.37 0.54 Hog Fuel 1.13 0.35

Unwanted Characteristics of Bio-oil

Attribute Problem

Low pH Corrosion

High viscosity Handling, pumping

Instability Storage, phase separation, polymerization, viscosity increase

Solids content Combustion problems, equipment blockage, erosion

Alkali metals Deposition of solids in boilers, engines, and turbines

Water content Complex effect on heating value, viscosity, pH, homogeneity, etc.

Bio-oil Components—Essentially all oxygenates

Carbohydrate fragments Anhydrosugars Sugar fragments

Carbonyls Hydroxyaldehydes

Furfurals Alcohols Acids

Acetic Formic Sugar acids

Lignin fragments Phenolics Aromatic ethers Methanol Oligomers

Refinery Drop-in points for Bio-Oil

Biomass Refinery-Ready Intermediates

Near-Fuels and Blendstocks

Research Areas

Existing Refinery Infrastructure

Gasoline Jet Fuel

Diesel Fuel Crude

Oil Drop-In Fuels

Drop in Point #1: Pyrolysis

Oil

Drop in Point #3:

Fuels Blendstock

Drop in Point #2:

Stable Oil

Atm

osph

eric

and

Va

cuum

Dis

tilla

tion Gas

Light Naphtha Heavy

Naphtha LGO VGO

Atm. Res. Vac. Res.

Reform

FCC

Alky/Poly

HT/HC

Coker

PIP

ELI

NE

EDOx Pyrolysis Process

Modified from www.honeywellnow.com

EDOx OXYGEN

EDOx GREEN FUEL

Path Forward-Ceramatec/PNNL project Bio-oil vapor conversion to liquid fuels via EDOx process needs to be demonstrated

Appropriate model compounds Mixed model compounds Bio-oil vapor components

Process design for bench-scale demonstration needs to be developed Bench-scale processing of hot vapor from fast pyrolysis by EDOx needs to be evaluated

Deox Process Overview

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“Deoxygenation” Background

• 25 Years of Solid Oxide Fuel Cells – Fuel: hydrogen, syngas from reformed

methane, JP-8 – kW class demonstration

• 10 Years of Solid Oxide Electrolysis Cells – Electrolysis of steam to generate hydrogen – Co-electrolysis of steam, carbon dioxide

mixture to generate syngas – 17 kW demonstration at Idaho Natl Lab.

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Deoxygenation Process

• Doped (Y or Sc) Zirconia membrane – Oxygen ion conductor – No other ions move through – 100% of current is from oxygen transport

• 100% Current (Faradaic) efficiency

• Air electrode (Perovskite) • Fuel electrode (Ni-Ceria cermet)

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Electrolysis Of CO2 Feed: H2O, CO2, (minor H2, CO) Reactions: Oxygen removal from steam, CO2, and Reverse Shift Reverse Shift Reaction: CO2 + ⇑ H2 <==> CO + ⇓ H2O

O= flux

Oxygen Product Flow

CO, CO2

H2, H2O

CO, CO2

H2, H2O

} Rev. Shift CO, CO2

H2, H2O { CO, CO2

H2, H2O

Button Cell

• Single Cell (Anode/Electrolyte/Cathode)

• Oxygenated Species on cathode side (inside the tubular manifold)

• Air flow on the anode side

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Reactor for feasibility tests

Short Stack Configuration

Possible Scale up options

720 Cell System at INL 5.7 Nm3/hr - 17.5kW H2 Production

Overall Process Schematic

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The overall pyrolysis oil to liquid hydrocarbons system without using hydrogen

Hypothesis

• Can we remove oxygen from oxygenated hydrocarbon directly or indirectly?

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Direct: Electrochemical transport of oxygen directly Indirect: Electrochemical transport of oxygen from water to create hydrogen in-situ to deoxygenate hydrocarbon

Benefits • Deoxygenation prior to cooling of bio-

vapors • Electrochemical reaction only removes

oxygen (every 4 electrons in the circuit removes one molecule of oxygen) – All C and H are retained on the fuel side – Lighter HC with fuel value as co-product

• No hydrogen required • Temperature compatibility (EDOx ~ 650-700°C)

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Initial Experiment • Model Compound Acetone

– Dilute Acetone vapor (N2 bubbled through acetone liquid)

– Hydrogen bubbled through water (to keep Ni reduced) • Test Condition: 650 °C, 30 to 50 mA/cm2

• Under current the exit gas contained methane (~70%), other hydrocarbon – ethane mainly, and some evidence of octane - (10%)

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Challenges • Would Ni promote coking, formation of large

amount of syngas? – Will investigate coke-resistance cathode compositions

• Regeneration of electrode after fouling • Conversion at ambient pressure, and recycle

requirements • Module design • Separator/current collector (protective layer for

metal plates?)

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Model Compound Selection

• Simple to Complex – Aldehydes, Ketones, Acids, Phenol – Mixtures – Bio-oil vapor

• Button Cell to multi-cell reactor • Integrated test at PNNL

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Other Fuel Synthesis Projects

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Ceramatec’s Decarboxylation Process

• No hydrogen addition • Enables distributed manufacturing

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𝟐𝟐𝟐𝑶𝟐𝑵𝑵 → 𝟐 −𝟐 + 𝟐𝟐𝑶𝟐 + 𝟐𝒆− + 𝟐𝑵𝑵+

Conversion to Sodium

Salts

CDP Electrochemical

Process

Sodium Recycle

Products

CO2 Evolution

H2 Evolution

Carboxylic Acid precursors

Modified Kolbe Electrolysis

Decarboxylation Technology

• Description: – NaSICON electrolytic

cell used to produce hydrocarbons from fatty acids

• Applications: – Chemicals production – Lubricant production – Fuels production

• Status:

- Laboratory investigation on-going

Na salt of fatty acid + solvent

Hydrocarbon + solvent

Anode

Cathode

Na scavenger

Na recycle

CO2

Ion transport

2R-COONa --------- > R-R + 2CO2 + 2e- + 2Na+

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Decarb Module

• Currently testing single membrane – Vary starting

hydrocarbon – Product Selectivity – Yield – Operating conditions – Lifetime

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Other Fuel Synthesis Projects

Reformation of Tars & Oils from Biogas

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Air or Oxygen

Gasification Unit

Clean Synthesis Gas

Electric Power Generation

Fischer Tropsch synthesis

Methanation

Non-thermal Plasma

Reformer

Biomass or Other feed

Directly reform tars & oils

Reheat Air or Oxygen

Laboratory scale plasma reformer

Simulated gasifier stream Bottled syngas Toluene injection Steam, O2, or air to obtain

temperature GC analysis of toluene

destruction and CGE

Best combination

Dry Gas Air In O2 In H2O In Toluene In

Run L/min L/min L/min g/min g/min

4 50 52 0 1.7 5.9

Mole % Output

Run H2 N2 CO CO2 Toluene CH4 H20

4 12 54 21 7 0 .3 6

LHV Gas In LHV Gas Out Thermal Eff Toluene

Run kW kW Percent % Destroyed

4 5.02 5.87 117 100

• Run 4 had good destruction and good efficiency

Excellent Conversion Obtained

• Conversion of BTX and other hydrocarbons very good – 92% methane (near equilibrium limit) – 96% ethane – 100% (to detection limit) of other C2-C4 – 98% benzene – 99% toluene – 100% (to detection limit) of xylenes

Process design basis

• Basis process feed: 500 SCFM • Gasifier product composition from Emery Energy • Ability to add O2 or air

• to provide heat of reformation • raise temperature to 850ºC • 17.9 SCFM of O2 required to raise T from 504oC to 850oC

• No coke is detected (sufficient steam present)

Reformer installation

• Assembled 3-stage reformer • At Western Research Institute – Laramie, WY • Installed and tested

Other Fuel Synthesis Projects

Syngas to Liquid

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Biogas to Fuel Capabilities

Biogas

Sulfur Tolerant Reformer

Syngas

Fischer- Tropsch

Transportation Fuels

Compression & Storage

Ceramatec Laboratory FT System

Capacity: 3 to 4 liters/day Single tube FT reactor 42.7mm ID, 2.0 m length, ~2.9 liters Backpressure regulation system, 20-30 barg High pressure mass flow controllers (low/high range) Temperature controllers for reactor and collection system Hot and cold product collection vessels Recycle pump & Cooling system

Ceramatec FT Product From 1-1/2” Reactor

• Production rates up to 4 liter/day

• 2200 hour run

• FT 46.5 MJ/kg, diesel 46 MJ/kg, 40 MJ/kg B100 FAME

• Cetane 60.2 by ASTM D613

Pre-pilot Plant Scale up

4” Reactor Tube - Fischer Tropsch Skid

FT Demonstration

30 liters/day FT Production Demonstrated

Product Collection

FT Product Analysis

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02468

1012141618

5 15 25 35

%C

N

Carbon Number

081913 090613 091013 091613 091813 091213091313 100113 100313 100213 093013 092613092513 092413 092313 092013

Summary

• Ceramatec has been investigating transportation fuel synthesis options for over a decade

• Currently three major projects at various TRL underway – Deoxygenation of Bio-oil – Decarboxylation of fatty acids from bio-source – Biogas clean up and FT conversion to liquids

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